Technical field
[0001] The present invention relates to cleaning compositions. More particularly, the cleaning
compositions according to the present invention are stable aqueous emulsions particularly
suitable to be used in laundry applications for example as detergent compositions
or as pre-wash treating compositions or as laundry additives to be used together with
detergents.
Background
[0002] A great variety of cleaning compositions have been described in the art. A problem
associated with common cleaning compositions is that they do not allow to deliver
whitening performance which satisfactorily meet consumer's needs, when used in laundry
application to treat different kind of fabrics, especially when used to treat synthetic
fabrics such as polyesters, polyamides and the like.
[0003] It is therefore an object of the present invention to provide compositions suitable
for use in laundry application, whereby the whiteness to synthetic fabrics is improved.
It is a further object of the present invention to provide such compositions which
can be satisfactorily used for treating various types of fabrics and clean various
types of stains while providing at the same time also good fabric safety to the fabrics
treated therewith. Also said compositions should provide improved whitening performance
to synthetic fabrics under most common wash conditions including conditions under
which the wash temperature is low, i.e. below 60° C.
[0004] We have now found that these objects can be efficiently met by formulating aqueous
compositions comprising a hydrophobic brightener wherein said hydrophobic brightener
is emulsified in said compositions by a surfactant system comprising at least a hydrophobic
surfactant having an HLB (Hydrophilic lipophilic balance) up to 9 and at least a hydrophilic
surfactant having an HLB above 10. In other words, it has been found that the present
invention through a formulation of a hydrophobic brightener, i.e. a brightener whose
solubility in water is lower than 5 grams per liter at 25°C, into an emulsion allows
to exploit the benefits associated with said brightener, e.g. whitening performance
improvement of synthetic items such as polyesters, polyamides and the like. Indeed,
the compositions of the present invention allow to incorporate and to deliver hydrophobic
brighteners into the wash solution, this under the most common wash conditions, e.g.
below 60°C. Formulating such hydrophobic brighteners through liquid compositions being
not emulsions or even through powder formulations does not allow to obtain the outstanding
whitening performance associated with the present invention.
[0005] An advantage associated with the formulation of hydrophobic brighteners through emulsions
is that said brighteners also contribute to the multi-cycle whitening of cotton fabrics.
Indeed, after several wash cycles cotton fibers assume a partially hydrophobic character
due for example of deposition of organic species on the fabric surface, i.e. a hydrophobic
layer of soils tend to form onto aged fabrics, and thus they become sensitive to hydrophobic
brighteners. The hydrophobic brighteners may thus absorb onto said cotton fibers,
adsorb UV light and retransmit visible blue light so providing superior whiteness.
[0006] Another advantage of the compositions of the present invention is that in addition
to their outstanding whitening action said compositions allow also good stain removal.
Indeed, the use of hydrophobic surfactants to emulsify said hydrophobic brighteners
provides excellent hydrophobic soil removal and good grease cutting properties.
[0007] A further advantage of the present invention is that it allows for great flexibility
in formulating and provides compositions being chemically and physically stable and
suitable to be used in the most efficient manner by the consumer. The preferred compositions
therein comprise hydrogen peroxide.
[0008] Another advantage of such compositions is that they provide a means to formulate
ingredients with very low water solubility, without the need for using alcoholic or
solvent mixtures, which are usually undesirable for aesthetic (odor) and toxicity
reasons.
[0009] Yet another advantage of the present invention is that hydrophobic brighteners, such
as Tinopal SOP ® give to said compositions a perleascent color that improves the product
aesthetics.
[0010] Cleaning compositions comprising optical brighteners have been disclosed in the art.
For instance, EP-A-598973 discloses a composition comprising hydrogen peroxide and
as a surfactant, a fully nonionic system, i.e. at least one nonionic with an HLB above
15, at least one nonionic with an HLB of from 13 to 15, at least one nonionic with
an HLB of from 9 to 13 and at least one nonionic with an HLB below 9. This patent
application further discloses the use of Tinopal CBS X® (4-4'-bis (2-2' styryl sulfonate)
biphenyl) as an optical brightener. However, this patent application differs from
the present invention in that the compositions disclosed therein are not emulsions
and in that the hydrophobic brighteners of the present invention are nowhere mentioned
therein. Indeed, Tinopal CBS X®, also named Brightener 49®, is a hydrophilic brightener
having a solubility of 30 grams per liter at 25°C in deionized water.
[0011] EP-A-598170 discloses emulsions of at least one hydrophobic nonionic surfactant and
at least one hydrophilic nonionic surfactant, said emulsions further comprise hydrogen
peroxide, or a source thereof. The invention disclosed in the '170 patent application
allows to formulate compositions comprising H₂O₂ and a hydrophobic bleach activator
(ATC), wherein said bleach activator is kept separate from H₂O₂. The pH of said emulsions
is from 1 to 5. This patent application further discloses the use of optical brighteners
as optional ingredients and mentions Brightener 49® in an example. Brightener 49®
is not a brightener being almost insoluble in water, i.e. a hydrophobic brightener
whose solubility in water is lower than 5 grams per liter at 25°C.
Summary of the invention
[0012] The present invention is an aqueous emulsion comprising at least a hydrophilic surfactant
having an HLB above 10 and at least a hydrophobic surfactant having an HLB up to 9,
said aqueous emulsion further comprises a hydrophobic brightener whose solubility
in water is lower than 5 grams per liter at 25 °C, or mixtures thereof.
[0013] The present invention also encompasses a method of bleaching or washing fabrics,
especially fabrics having a hydrophobic character such as synthetic fabrics to improve
fabrics whiteness.
[0014] The present invention also encompasses a process for the manufacture of said emulsions.
Detailed description of the invention
[0015] The compositions according to the present invention are stable aqueous emulsions
of surfactants which further comprise a hydrophobic brightener whose solubility in
water is lower than 5 grams per liter at 25°C. By "stable emulsion" it is meant an
emulsion which does not substantially separate into distinct layers, upon standing
for at least two weeks at 50 °C.
[0016] As an essential element, the compositions of the present invention comprise a surfactant
system of at least two different surfactants, i.e. at least a hydrophobic surfactant
having an HLB up to 9 and at least a hydrophilic surfactant having an HLB above 10
in order to emulsify the hydrophobic brightener. Indeed, said two different surfactants
in order to form emulsions which are stable must have different HLB values (hydrophilic
lipophilic balance), and preferably the difference in value of the HLBs of said two
surfactants is at least 1, preferably at least 3. In other words, by appropriately
combining at least two of said surfactants with different HLBs in water, emulsions
according to the present invention will be formed.
[0017] Said surfactant system makes the compositions able to incorporate a hydrophobic brightener,
i.e. a compound being almost insoluble in water medium, and to delivery it into the
wash solution as a finely dispersed liquid. Indeed, the present invention allows to
exploit the benefits associated with a hydrophobic brightener otherwise not exploitable
under common wash conditions, i.e. below 60°C, either through liquid or powder formulation.
[0018] The compositions according to the present invention comprise from 2% to 50% by weight
of the total composition of said hydrophilic and hydrophobic surfactants, preferably
from 5% to 40% and more preferably from 8% to 30%. The compositions according to the
present invention comprise at least from 0.1% by weight of the total composition of
said hydrophobic surfactant, or mixtures thereof, preferably at least 3% and more
preferably at least 5% and at least from 0.1% by weight of the total composition of
said hydrophilic surfactant, or mixtures thereof, preferably at least 3% and more
preferably at least 6%.
[0019] Preferred to be used herein are the hydrophobic nonionic surfactants and hydrophilic
nonionic surfactants. Said hydrophobic nonionic surfactants to be used herein have
an HLB up to 9, preferably below 9, more preferably below 8 and said hydrophilic surfactants
have an HLB above 10, preferably above 11, more preferably above 12. Indeed, the hydrophobic
nonionic surfactants to be used herein have excellent grease cutting properties, i.e.
they have a solvent effect which contributes to hydrophobic soils removal. The hydrophobic
surfactants act as carrier of the hydrophobic brighteners onto the fabrics allowing
thereby said brighteners to work in close proximity with the fabrics surface since
the beginning of the wash.
[0020] Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols preferably,
fatty alcohol ethoxylates and/or propoxylates. Indeed, a great variety of such alkoxylated
fatty alcohols are commercially available which have very different HLB values (hydrophilic
lipophilic balance). The HLB values of such alkoxylated nonionic surfactants depend
essentially on the chain length of the fatty alcohol, the nature of the alkoxylation
and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high
degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants
tend to have a low degree of alkoxylation and a long chain fatty alcohol. Surfactants
catalogues are available which list a number of surfactants including nonionics, together
with their respective HLB values.
[0021] Suitable chemical processes for preparing the nonionic surfactants for use herein
include condensation of corresponding alcohols with alkylene oxide, in the desired
proportions. Such processes are well known to the man skilled in the art and have
been extensively described in the art. As an alternative, a great variety of alkoxylated
alcohols suitable for use herein is commercially available from various suppliers.
[0022] Preferred hydrophobic nonionic surfactants to be used in the compositions according
to the present invention are surfactants having an HLB up to 9 and being according
to the formula RO-(C₂H₄O)
n(C₃H₆O)
mH, wherein R is a C₆ to C₂₂ alkyl chain or a C₆ to C₂₈ alkyl benzene chain, and wherein
n+m is from 0.5 to 5 and n is from 0 to 5 and m is from 0 to 5 and preferably n+m
is from 0.5 to 4 and, n and m are from 0 to 4. The preferred R chains for use herein
are the C₈ to C₂₂ alkyl chains. Accordingly suitable hydrophobic nonionic surfactants
for use herein are Dobanol
R 91-2.5 (HLB= 8.1; R is a mixture of C₉ and C₁₁ alkyl chains, n is 2.5 and m is 0),
or Lutensol
R TO3 (HLB=8; R is a mixture of C₁₃ and C₁₅ alkyl chains, n is 3 and m is 0), or Tergitol
R 25L3 (HLB= 7.7; R is in the range of C₁₂ to C₁₅ alkyl chain length, n is 3 and m
is 0), or Dobanol
R 23-3 (HLB=8.1; R is a mixture of C₁₂ and C₁₃ alkyl chains, n is 3 and m is 0), or
Dobanol
R 23-2 (HLB= 6.2; R is a mixture of C₁₂ and C₁₃ alkyl chains, n is 2 and m is 0), or
mixtures thereof. Preferred herein are Dobanol
R 23-3, or Dobanol
R 23-2, Lutensol
R TO3, or mixtures thereof. These Dobanol
R surfactants are commercially available from SHELL. These Lutensol
R surfactants are commercially available from BASF and these Tergitol
R surfactants are commercially available from UNION CARBIDE.
[0023] Other suitable hydrophobic nonionic surfactants to be used herein are non alkoxylated
surfactants. An example is Dobanol 23 (HLB<3 ).
[0024] Preferred hydrophilic nonionic surfactants to be used in the compositions according
to the present invention are surfactants having an HLB above 10 and being according
to the formula RO-(C₂H₄O)
n(C₃H₆O)
mH, wherein R is a C₆ to C₂₂ alkyl chain or a C₆ to C₂₈ alkyl benzene chain, and wherein
n+m is from 5 to 11 and n is from 0 to 11 and m is from 0 to 11, preferably n+m is
from 6 to 10 and, n and m are from 0 to 10. Throughout this description n and m refer
to the average degree of the ethoxylation/propoxylation. The preferred R chains for
use herein are the C₈ to C₂₂ alkyl chains. Accordingly suitable hydrophilic nonionic
surfactants for use herein are Dobanol
R 23-6.5 (HLB=11.9 ; R is a mixture of C₁₂ and C₁₃ alkyl chains, n is 6.5 and m is
0), or Dobanol
R 25-7 (HLB=12 ; R is a mixture of C₁₂ to C₁₅ alkyl chains, n is 7 and m is 0), or
Dobanol
R 45-7 (HLB=11.6 ; R is a mixture of C₁₄ and C₁₅ alkyl chains, n is 7 and m is 0),
or Dobanol
R 91-5 (HLB=11.6 ; R is a mixture of C₉ to C₁₁ alkyl chains, n is 5 and m is 0), or
Dobanol
R 91-6 (HLB=12.5 ; R is a mixture of C₉ to C₁₁ alkyl chains, n is 6 and m is 0), or
Dobanol
R 91-8 (HLB=13.7; R is a mixture of C₉ to C₁₁ alkyl chains, n is 8 and m is 0), or
Dobanol
R 91-10 (HLB= 14.2 ; R is a mixture of C₉ to C₁₁ alkyl chains, n is 10 and m is 0),
or mixtures thereof. Preferred herein are Dobanol
R 91-10, or Dobanol
R 45-7, Dobanol
R 23-6.5, or mixtures thereof . These Dobanol
R surfactants are commercially available from SHELL.
[0025] Apart from the hydrophilic nonionic surfactants other hydrophilic surfactants may
further be used in the present invention such as anionic surfactants, in particular
sulfonate and sulfate surfactants. The like anionic surfactants are well-known in
the art and have found wide application in commercial detergents. These anionic surfactants
include C8-C22 alkyl benzene sulfonates (LAS), C8-C22 alkyl sulfates (AS), unsaturated
sulfates such as oleyl sulfate, C10-C18 alkyl alkoxy sulfates (AES) and C10-C18 alkyl
alkoxy carboxylates. The neutralizing cation for the anionic synthetic sulfonates
and/or sulfates is represented by conventional cations which are widely used in detergent
technology such as sodium, potassium or alkanolammonium. Preferred herein are the
alkyl sulphate, or mixtures thereof, especially sodium alkyl sulphate having from
10 to 16 carbon atoms in the alkyl chain, preferably from 12 to 14.
[0026] The compositions according to the present invention may further comprise other surfactants
which should however not significantly alter the weighted average HLB value of the
overall composition.
[0027] As a further essential element the compositions according to the present invention
comprise a hydrophobic brightener, or mixtures thereof. Brighteners are compounds
which have the ability to fluorescent by absorbing ultraviolet wave-lengths of light
and re-emitting visible light. Brighteners, also referred to as fluorescent whitening
agent (FWA), have been extensively described in the art, see for instance EP-A-0 265
041, EP-A-0 322 564, EP-A-0 317 979 or "Fluorescent whitening agents" by A.K. Sarkar,
published by MERROW, especially page 71-72. Said brighteners are substituted stilbenes
and biphenyls such as but not limited to polycyclic oxazole derivatives, styryl stilbene
derivatives, aryltriazole derivatives, or mixtures thereof. By hydrophobic brightener
it is to be understood herein any brightener whose solubility in water is lower than
5 grams per liter at 25°C. Said hydrophobic brighteners to be used herein preferably
have a solubility in water being lower than 3 and more preferably being lower than
1. By "solubility" of a given compound it is to be understood herein the amount of
said compound solubilized in deionized water at 25°C. Thus, a compound having a solubility
being lower than 5 grams per liter means that when less than 5 grams of said given
compound is incorporated in deionized water at 25°C said compound is entirely dissolved
in said water, i.e. a clear and stable solution is obtained. In other words, incorporating
5 grams per liter or more of said given compound in water will result in a precipitation
of said compound in said medium.
[0028] Typically, the compositions according to the present invention comprise from 0.02%
to 1% by weight of the total composition of said hydrophobic brightener, preferably
from 0.05% to 0.5% and more preferably from 0.05% to 0.2%.
[0029] Preferred hydrophobic brighteners for use herein are styryl stilbene derivatives,
or aryltriazole derivatives, or polycyclic oxazole derivatives such as benzo-oxazole
derivatives, or mixtures thereof and particularly preferred herein are benzo-oxazole
derivatives. An example of such a brightener is benzoxazole,2,2'- (thiophenaldyl)bis
having the following formula C18H10N2O2S, commercially available from Ciba-Geigy under
the trade name Tinopal SOP®. This brightener is almost insoluble in water, i.e. it
has a solubility being lower than 1 gram per liter.
[0030] In another embodiment of the present invention the compositions herein further comprise
a hydrophilic brightener, or mixtures thereof. By hydrophilic brightener it is to
be understood herein any brightener whose solubility in water is higher than 10 grams
per liter at 25°C. Said hydrophilic brighteners to be used herein preferably have
a solubility in water being higher than 15 and more preferably being higher than 20.
Typically, the compositions according to the present invention comprise from 0% to
1% by weight of the total composition of said hydrophilic brightener, preferably from
0% to 0.5% and more preferably from 0% to 0.2%.
[0031] Such hydrophilic brighteners for use herein are the substituted stilbenes and biphenyls
in general such as substituted stilbene 2,2'-disulfonic acid derivatives having a
solubility in water higher than 10 grams per liter at 25°C. An example of such a brightener
is 4-4'-bis (2-2' styryl sulfonate) biphenyl, commercially available from Ciba-Geigy
under the trade name Brightener 49®. Other hydrophilic brighteners suitable to be
used herein are for example Brightener 3® or Brightener 47®, also commercially available
from Ciba-Geigy.
[0032] The compositions according to the present invention are aqueous. Accordingly, the
compositions according to the present invention comprise from 10% to 95% by weight
of the total composition of water, preferably from 30% to 90%, most preferably from
60% to 80%. Deionized water is preferably used.
[0033] It has been found that the pH of the formulation influences its stability. Other
than this, there are no other limitations in the pH of the composition. However, bleaching
ingredients being optional but preferred ingredients of the compositions herein, it
is of course necessary, for chemical stability purpose to formulate the compositions
herein with bleaches at a pH as is of from 0 to 6, preferably of from 0.5 to 5 and
more preferably from 0.5 to 4. The pH of the composition can be trimmed by all means
available to the man skilled in the art.
[0034] Accordingly, preferred compositions according to the present invention comprise bleaches,
i.e. hydrogen peroxide or a water-soluble source thereof. Suitable water-soluble sources
of hydrogen peroxide include perborate, percarbonate, persilicate and persulphate
salts. Hydrogen peroxide is most preferred to be used in the compositions according
to the present invention. Typically, the compositions according to the present invention
comprise from 0.5% to 20% by weight of the total composition of hydrogen peroxide,
preferably from 2% to 15%, most preferably from 3% to 10%.
[0035] Preferred compositions according to the present invention may further comprise a
bleach activator. By bleach activator, it is meant herein any compound which reacts
with hydrogen peroxide to form a peracid. In the case of bleach activators, such hydrophobic
bleach activators typically belong to the class of esters, amides, imides, or anhydrides.
A particular family of bleach activators of interest in the present invention were
disclosed in applicant's co-pending European patent application No 91870207.7. Particularly
preferred in that family is acetyl triethyl citrate which was also disclosed in the
context of bar soaps in FR 2 362 210. Acetyl triethyl citrate has the advantages that
it is environmentally friendly as it eventually degrades into citric acid and alcohol.
Furthermore, acetyl triethyl citrate has a good hydrolytical stability in the product
upon storage and it is an efficient bleach activator. Other bleach activators to be
used in the present invention are lactam derivatives. As used herein and unless otherwise
specified, the term bleach activator includes mixtures of bleach activators.
[0036] The compositions according to the present invention may further comprise the usual
optional ingredients such as perfumes, dyes, builders, chelants, pigments, enzymes,
dye transfer inhibitors, solvents, buffering agents and the like.
[0037] In the present invention, wherein the compositions comprise a hydrophobic brightener
having a solubility in water being lower than 5 grams per liter, i.e. being almost
insoluble in water, the surfactant system to be chosen to emulsify said hydrophobic
brightener depends on the HLB value of said brightener. Accordingly, a suitable way
to proceed is to determine the HLB value of the hydrophobic ingredient (brightener),
then select both the hydrophobic surfactants which have HLB values below said HLB
value of said hydrophobic ingredient and the hydrophilic surfactants which have HLB
values above said HLB value of said hydrophobic ingredient, wherein the difference
in the HLB values of said hydrophobic and hydrophilic nonionic surfactants is at least
1, preferably at least 3.
[0038] In a preferred embodiment comprising said hydrophobic brightener which is a hydrophobic
ingredient, the emulsifying system meets the equation:

where X refers to the hydrophobic ingredient to emulsify if several hydrophobic ingredients
are present X refers to all of them, A refers to one of said nonionic surfactants
(hydrophilic or hydrophobic), and B refers to the other said nonionic surfactant (hydrophilic
or hydrophobic).
[0039] In a particularly preferred embodiment of the present invention, wherein the compositions
comprise Acetyl triethyl citrate as the bleach activator and the hydrophobic brightener,
an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant
with for instance an HLB of 6, such as a Dobanol
R 23-2 and a hydrophilic nonionic surfactant with for instance an HLB of 15, such as
a Dobanol
R 91-10. Other suitable nonionic surfactant systems comprise for example a Dobanol
R 23-6.5 (HLB about 12) and a Dobanol
R 23 (HLB below 6) or a Dobanol
R 45-7 (HLB=11.6) and Lutensol
R TO3 (HLB=8).
[0040] The compositions of the present invention allow to achieve improved whitening performance
on hydrophobic-type of fabrics, i.e. synthetic fabrics such as polyesters, polyamides
and the like. By "improved whitening performance" it is meant herein that the whiteness
on fabrics (synthetic) achieved by using a composition comprising a hydrophobic brightener
emulsified by a surfactant system of at least one hydrophobic surfactant and at least
one hydrophilic surfactant is improved, as compared to the whiteness obtained by using
the same composition with a hydrophilic brightener instead of said hydrophobic one
as herein defined. Also through the formulation into an emulsion the hydrophobic brightener
is delivered into the wash as a finely dispersed liquid and thus is active at low
temperature used in common wash conditions (below 60°C). More particularly the compositions
of the present invention which further comprise a hydrophilic brightener as defined
herein allow to achieve improved whitening performance on all kinds of fabrics (cotton
natural fibers as well as synthetic and mixed fabrics) as compared to the same compositions
comprising only said hydrophilic brightener as the brightener.
[0041] A further advantage associated with the compositions of the present invention comprising
a hydrophobic brightener emulsified in a surfactant system as described herein is
that said hydrophobic brightener may contribute to the multi-cycle whitening of cotton
fibers even in absence of any hydrophilic brightener which are known to be particularly
effective on cotton fabrics. Aged cotton fabrics become partially hydrophobic, i.e.
they are covered by thin hydrophobic layers of soils such as deposition of organic
materials thus becoming sensitive to hydrophobic brighteners.
[0042] The present invention further encompasses a process for the manufacture of the composition
described herein. The process according to the present invention comprises at least
three steps:
In the first step, a hydrophobic mixture is prepared which comprises at least said
hydrophobic nonionic surfactant and hydrophobic brightener. Said hydrophobic mixture
may further comprises other hydrophobic ingredients which are to be formulated in
the composition, such as perfumes, solvents, enzymes, bleach activators and polymers.
[0043] In the second step, a hydrophilic mixture is prepared which comprises at least said
water, and said hydrophilic nonionic surfactant. Said hydrophilic mixture preferably
further comprises other hydrophilic ingredients which are to be formulated in the
composition such as dyes, hydrophilic optical brighteners, builders, chelants, hydrogen
peroxide and buffering agents. In this second step hydrogen peroxide when present
is preferably added last, after said buffering agent has been added.
Naturally, said first and said second steps can be performed in any order, i.e. second
step first is also suitable.
[0044] In the third step of the process according to the present invention, said hydrophobic
mixture and said hydrophilic mixture are mixed together.
[0045] The compositions according to the present invention are particularly useful as laundry
detergent or as laundry pretreaters, i.e. compositions which are dispensed and left
to act onto fabrics before they are washed, or as laundry additives to be used together
with detergents to boost their performance. Indeed, the compositions of the present
invention may be incorporated per se in any type of detergents including detergents
being in a liquid or a granular form. The technologies used to incorporate the compositions
of the present invention in a detergent being in a granular form are those commonly
known to those skilled in the art like spraying and/or encapsulation.
[0046] The present invention further encompasses a method of bleaching and/or washing fabrics
wherein a composition as defined hereinbefore is contacted with said fabrics. More
specifically, in the preferred embodiment of the present invention where the compositions
of the present invention comprise bleaches, the method of bleaching fabrics to improve
fabric whiteness comprises the steps of first contacting said fabrics with a composition
of the present invention, then allowing said fabrics to remain in contact with said
composition, for a period of time sufficient to bleach said fabrics, typically 2 to
60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics in water to remove
said composition. If said fabrics are to be washed, i.e. with a conventional composition
comprising at least one surface active agent, it is preferred to perform the method
herein before said fabrics are washed. Indeed, it has been observed that bleaching
said fabrics with the compositions according to the present invention prior to washing
them with a detergent composition provides superior whiteness and stain removal with
less energy and detergent than if said fabrics are washed first, then bleached. Accordingly,
said method according to the present invention further comprises a subsequent step
where said fabrics are washed with a detergent composition comprising at least one
surface active agent.
[0047] The present invention will be further illustrated by the following examples.
1) Experimental data
[0048] Compositions are made which comprise the listed ingredients in the listed proportions
(weight %).
| Compositions |
I |
II |
III |
IV |
| Dobanol R 45-7 |
6 |
6 |
6 |
6 |
| Dobanol R 91-10 |
3 |
3 |
3 |
3 |
| Dobanol R 23-2 |
6 |
6 |
6 |
6 |
| Hydrogen peroxide |
7.5 |
7.5 |
7.5 |
7.5 |
| Acetyl triethyl citrate |
7.0 |
7.0 |
7.0 |
7.0 |
| Brightener R 49 |
---- |
---- |
0.1 |
0.1 |
| Tinopal SOP R |
---- |
0.1 |
---- |
0.1 |
| S,S-ethylene diamino |
|
|
|
|
| disuccinic acid |
0.1 |
0.1 |
0.1 |
0.1 |
| Poly(4-vinylpyridine- |
|
|
|
|
| N-oxyde) |
0.1 |
0.1 |
0.1 |
0.1 |
| HOES R 3639 |
0.2 |
0.2 |
0.2 |
0.2 |
| Silicon |
0.2 |
0.2 |
0.2 |
0.2 |
| Deionized water |
--------------balance-------------- |
Citric acid up to pH 4
HOES R 3639 is a terephthalate based polymer commercially available from Hoechst. |
[0049] Composition I is an emulsion taken as reference in the following test and comprises
no brighteners at all.
[0050] Compositions II and IV are representative of the present invention. Composition II
is an emulsion of nonionic surfactants comprising among other hydrogen peroxide, a
bleach activator (ATC) and a hydrophobic brightener, Tinopal SOP®. Composition IV
differs from composition II in that it further comprises a hydrophilic brightener,
Brightener 49®.
[0051] Composition III is a composition representative of the prior art, i.e. an emulsion
of nonionic surfactants comprising hydrogen peroxide and a bleach activator (ATC)
and as a brightener a hydrophilic brightener.
[0052] A single tracer launderometer test was carried out by using said bleaching compositions
mentioned above followed by the use of a detergent composition.
[0053] The test was performed in a stainless steel vessel. First 2 ml of each of the above
bleaching compositions I to IV were diluted in 0.5 liters of tap water. The test was
carried out at 18°C. The tracers, i.e. fabrics such as clothes, towels and the like,
with standardized stains were added into the prepared solutions. The vessel was then
kept under agitation for 20 minutes. At the end of the washing cycle the tracers were
rinsed with water. Then, a detergent commercially available on the market (Dash Ultra®)
was used to wash the tracers. 5g of the detergent were diluted into 0.5 liter of tap
water. This solution was heated at 40°C. The vessel was then kept under agitation
for 20 minutes with the tracers. At the end of the washing cycle the tracers were
rinsed and dried. Then the tracers were evaluated by visual grading.
[0054] The table below lists the results in terms of whiteness obtained after one wash cycle
for compositions II, III and IV versus composition I on different kinds of fabrics,
polyester, cotton/polyester and cotton only. The table also gives the results in terms
of whiteness obtained after one wash cycle for composition I on top of which Tinopal
Sop
R was added as is directly in the wash solution at the beginning of the wash cycle
versus composition I used alone.
| |
Comp. I *vs. I |
Comp. II vs. I |
Comp. III vs. I |
Comp. IV vs. I |
| Polyester |
0 |
1.8S |
0 |
1.8S |
| Cotton/polyester |
0 |
1.0S |
1.2S |
2.0S |
| Cotton |
0 |
0.2 |
1.5S |
1.8S |
Where:
- Results are expressed on a 0 to 4 performance scale evaluated by expert judgment.
- S identifies statistically reproducible results. |
| * Tinopal Sop R was added as is on top of composition I in the wash solution at the beginning of
the wash cycle. |
Comments:
[0055] The data clearly shows significant whiteness improvement delivered by the compositions
of the present invention comprising a hydrophobic brightener emulsified by a nonionic
surfactant system. Indeed, after one wash cycle only the compositions according to
the present invention comprising a hydrophobic brightener emulsified in a nonionic
surfactant system (compositions II and IV) as compared to both a composition available
on the market comprising only a hydrophilic brightener as the brightener (composition
III) and to a composition wherein said hydrophobic brightener is not emulsified (composition
I*) but incorporated separately as is in the wash solution, provides better whitening
performance on synthetic fabrics, e.g. polyester. Said data also shows that the emulsions
of the present invention comprising a hydrophobic and a hydrophilic brightener provide
fabric whiteness improvement on various types of fabrics, polyester alone, cotton
alone or mixtures thereof as compared to the compositions available on the market
(see composition IV versus composition III).
2) Examples
[0056] Further examples of the compositions according to the present invention are the following.
These compositions are made comprising the listed ingredients in the listed proportions
(weight %):
| Compositions |
I |
II |
III |
| Dobanol R 45-7 |
6.7 |
6.0 |
6.0 |
| Lutensol T03 |
8.3 |
--- |
---- |
| Na alkyl sulphate |
2.0 |
--- |
---- |
| Dobanol R 23-2 |
---- |
6.0 |
6.0 |
| Dobanol R 91-10 |
---- |
3.0 |
3.0 |
| Hydrogen peroxide |
7.5 |
7.5 |
7.5 |
| Acetyl triethyl citrate |
7.0 |
7.0 |
7.0 |
| Brightener R 49 |
0.2 |
---- |
---- |
| Brightener R 3 |
---- |
0.2 |
---- |
| Brightener R 47 |
---- |
---- |
0.1 |
| Tinopal SOP R |
0.1 |
0.05 |
0.08 |
| S,S-ethylene diamino disuccinic acid |
---- |
0.1 |
0.1 |
| Diethylene triamine penta methylene phosphonic acid |
1.0 |
--- |
---- |
| Poly(4-vinylpyridine-N-oxyde) |
0.1 |
0.1 |
0.1 |
| HOES R 3639 |
0.2 |
0.2 |
0.2 |
| Silicon |
0.2 |
0.2 |
0.2 |
| Deionized water |
--------------balance-------------- |
| H2SO4 up to pH=4 |
[0057] Compositions I to III are each made by preparing two mixtures. A hydrophilic mixture
is prepared which comprises the hydrophilic ingredients such as water, hydrophilic
brightener, S,S-EDDS, poly(4-vinylpyridine-N-oxide), Dobanol
R 45-7, Dobanol
R 91-10, diethylene triamine penta methylene phosphonic acid or Na alkyl sulphate.
Hydrogen peroxide is added in said hydrophilic mixture as last step. A hydrophobic
mixture is prepared which comprises acetyl triethyl citrate, Dobanol
R 23-2, Lutensol T03, hydrophobic brightener, silicone or Hoes
R 3639. Then said hydrophobic mixture is poured into said hydrophilic mixture, while
mixing.
[0058] All the compositions according to the examples above are stable and provide excellent
whitening performance and safety to the fabrics treated with them while being also
efficient in removing stains. These advantages are observed when using said compositions
as a laundry composition or as an additive or as a pre-bleach associated with a detergent
composition.
1. An aqueous emulsion comprising at least a hydrophilic surfactant having an HLB above
10 and at least a hydrophobic surfactant having an HLB up to 9, characterized in that said aqueous emulsion further comprises a hydrophobic brightener whose solubility
in water is lower than 5 grams per liter at 25°C, or mixtures thereof.
2. An emulsion according to claim 1 wherein said hydrophobic brightener has a solubility
in water being lower than 3 grams per liter, preferably lower than 1 gram per liter.
3. An emulsion according to any of the preceding claims wherein said hydrophobic brightener
is an aryltriazole derivative, a styryl stilbene derivative, a polycyclic oxazole
derivative, or mixtures thereof, preferably a benzo-oxazole derivative and more preferably
said benzo-oxazole is benzoxazol,2,2'-(thiophenadyl)bis.
4. An emulsion according to any of the preceding claims wherein said emulsion comprises
from 0.02% to 1% by weight of the total emulsion of said hydrophobic brightener, preferably
from 0.05% to 0.5% and more preferably from 0.05 % to 0.2%.
5. An emulsion according to any of the preceding claims wherein said emulsion comprises
from 2% to 50% by weight of the total emulsion of said hydrophobic and hydrophilic
surfactants, preferably from 5% to 40% and more preferably from 8% to 30%.
6. An emulsion according to any of the preceding claims wherein said hydrophobic surfactant
is a nonionic surfactant, preferably a hydrophobic nonionic surfactant having an HLB
below 9, preferably below 8 and wherein said hydrophilic surfactant is a nonionic
surfactant, preferably a hydrophilic nonionic surfactant having an HLB above 11 ,
preferably above 12.
7. An emulsion according to any of the preceding claims wherein said emulsion further
comprises an anionic surfactant or mixtures thereof, preferably a sodium alkyl sulphate
having from 10 to 16 carbon atoms.
8. An emulsion according to any of the preceding claims which further comprises hydrogen
peroxide, or a water soluble source thereof and a bleach activator wherein said bleach
activator is emulsified by the surfactants.
9. An emulsion according to claim 8 which comprises from 0.5% to 20% by weight of the
total emulsion of said hydrogen peroxide.
10. An emulsion according to claims 8 and 9 wherein said bleach activator is acetyl triethyl
citrate.
11. An emulsion according to any of the preceding claims which further comprise a hydrophilic
brightener whose solubility in water is higher than 10 grams per liter at 25°C, preferably
higher than 15 grams per liter and more preferably higher than 20 grams per liter.
12. A detergent composition comprising an emulsion according to any of the preceding claims.
13. A process of bleaching or washing fabrics, especially fabrics having a hydrophobic
character such as synthetic fabrics, to improve fabric whiteness which comprises the
steps of:
- first contacting said fabrics with a composition or emulsion according to any of
the preceding claims,
- then allowing said fabrics to remain in contact with said composition or emulsion
for a period of time sufficient to bleach or wash said fabrics,
- then rinsing said fabrics in water to remove said composition or emulsion.
14. A process according to claim 13 which further comprises a subsequent step where said
fabrics are washed with a detergent composition comprising at least one surface active
agent.